The results of the innovative study on a new stationary phase with high efficiency based on ZnO nano and micro rod coating on fused silica are reported in this paper. ZnO nanorods with a diameter in the range of 70-300 nm and the length of about 500 nm, have been grown on fused silica fibers using a hydrothermal process. The extraction properties of the fiber were investigated using headspace solid-phase microextraction (HS-SPME) mode coupled with gas chromatography-mass spectrometry detection (GC-MS) for 1,4-dichloro-nitrobenzene, biphenyl and acenaphthene. The calibration curves were linear up to 10(2)-10(7) ng L(-1) (R(2)>0.995) with detection limits of 10(-3) ng L(-1) for biphenyl and acenaphthene and 10 ng L(-1) for 1,4-dichloro-nitrobenzene. The RSD for single fiber and fiber-to-fiber were less than 7.0 and 11.5%, respectively. The high stability of the ZnO coating is proved at relatively high temperatures (up to 300°C) with a high extraction capacity and long lifespan (more than 100 times). Promising recoveries (91-102%) were obtained in environmental water samples analysis by applying the proposed technique.